WO2006082733A1

WO2006082733A1 - Inkjet recording method using active energy ray-curable inkjet ink and inkjet recorder of active energy ray-curing type

Info

Publication number: WO2006082733A1
Application number: PCT/JP2006/301044
Authority: WO
Inventors: Nobumasa Sasa
Original assignee: Konica Minolta Medical & Graphic, Inc.
Priority date: 2005-02-01
Filing date: 2006-01-24
Publication date: 2006-08-10
Also published as: JPWO2006082733A1

Abstract

Disclosed is an inkjet recording method comprising a step for forming a pre-treatment layer on the surface of a base by performing a pre-treatment using a pre-treatment agent, and a step for recording wherein an active energy ray-curable inkjet ink is ejected onto the pre-treatment layer. This inkjet recording method is characterized in that the pre-treatment agent is a polymer latex. This recording method enables to obtain a high-quality printing, which has excellent adhesion to the base while being free from bleeding, with high productivity at low cost by using an active energy ray-curable inkjet ink. Also disclosed is a recorder which can be used for such an inkjet recording method.

Description

Specification

Ink jet recording method using active energy ray curable ink jet ink and active energy ray curable ink jet recording apparatus

Technical field

The present invention relates to a recording method for an active energy ray-curable inkjet ink and an active energy ray-curable inkjet recording apparatus used therefor.

Background art

In recent years, inkjet recording methods can create images easily and inexpensively, and thus have been applied to various printing fields such as photographs, various printing, marking, special printing such as color filters. In particular, a recording device that ejects and controls fine dots, an ink with improved color reproduction range 'durability' ejection suitability, and ink absorption / color development of colorant 'special paper with dramatically improved surface gloss It is also possible to obtain image quality comparable to silver halide photography. In other words, the image quality improvement of today's inkjet recording system is achieved only when all of the recording apparatus, ink, and special paper are available.

On the other hand, soft packaging is printed by a gravure printing method or a flexographic printing method. Gravure printing and flexographic printing are progressing at low cost and short delivery due to innovations in manufacturing methods. However, it takes a lot of time and cost to create a printing plate, and density stabilization after printing has started. Since it takes time to convert, small quantities of samples (prototypes, exhibitions, limited sales items, etc.) will result in a large amount of loss and a high unit price.

[0004] In addition, recently, there are some that can prepare samples for soft packaging films by the wet electrophotographic method. It takes time to adjust the level at start-up, and there is a problem with durability of printed images. It is not possible to deal with small lots efficiently.

[0005] Inkjet recording methods for soft packaging are generally recorded in black or white after packaging, and the date of manufacture, expiration date, etc. are recorded. It is not common to record images directly.

[0006] Also, in recent packaging, in order to draw out the concept and features of the product, various contrivances such as using mat packaging materials, making part of the mat substrate glossy, and vice versa. Has been helped. Furthermore, the required quality has been increasing year by year, such as high image quality and a feeling of incongruity.

[0007] Therefore, a method for recording an image on a film substrate by an inkjet method using UV (ultraviolet) curable ink has been studied. In general, there are various types of film substrates, and their wettability varies depending on the raw materials, additives, surface conditions, etc. of the substrates. In normal printing (mainly gravure printing), the ink and printing conditions are changed depending on the base material, or after the base material manufacturer performs pre-treatment such as corona treatment, it is used up within a certain period of time, or the corona treatment is performed immediately before. It corresponds with.

[0008] However, when using inkjet, changing the ink for each base material greatly impairs the ease and convenience of the ink jet, and the base material is used up within a certain period. However, even if there is no problem with gravure, etc. on the premise of mass printing, there is a lot of loss for inkjets aimed at small quantities and many types. Also, it is not practical to use pretreatment such as corona treatment for conventional printed matter because it significantly lowers the productivity of conventional printing presses.

[0009] Various improvement means have been studied for the above-mentioned problems. For example, a UV curable undercoat layer (see Patent Documents 1, 2, and 4), corona treatment, and plasma treatment (see Patent Document 3). It is disclosed. However, even with these proposed recording methods, it is quite possible to improve the above problems sufficiently.

Patent Document 1: Japanese Translation of Special Publication 2002-530229 (Claims)

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-211651 (Claims)

Patent Document 3: Japanese Patent Laid-Open No. 2003-237217 (Claims)

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-59810 (Claims)

Disclosure of the invention

Problems to be solved by the invention

[0010] The present invention has been made in view of the above-described problems, and an object of the present invention is to use an active energy ray-curable inkjet ink, to achieve high productivity, low cost, no bleeding, high image quality, and a base material. Active energy ray-curable inkjet ink recording method capable of printing with excellent adhesion and active energy ray-curable inkjet ink recording used therefor To provide an apparatus.

Means for solving the problem

The above object of the present invention is achieved by the following configurations.

1. Using a pretreatment agent on the surface of the substrate V to perform pretreatment ヽ Forming the pretreatment layer and discharging the active energy ray-curable inkjet ink onto the pretreatment layer and recording An ink jet recording method using an active energy ray-curable inkjet ink, characterized in that the pretreatment agent is a polymer latex.

2. The inkjet recording method using an active energy ray-curable inkjet ink according to 1, wherein the polymer latex contains a polymer compound having a cationic polymerization reactive group.

3. The ink jet recording method using the active energy ray-curable ink jet ink according to 1 or 2, characterized in that the active energy ray curable ink jet ink force contains a cationically polymerizable compound.

4. The cationically polymerizable compound is at least one selected from the group consisting of an oxetane ring-containing compound, an oxysilane group-containing compound, and a bull ether compound. An inkjet recording method using the active energy ray-curable inkjet ink according to the item.

5. The inkjet recording method using the active energy ray-curable inkjet ink according to any one of 1 to 4, which comprises the active energy ray-curable inkjet ink force and a light-power thione polymerization initiator.

6. The inkjet recording method using an active energy ray-curable inkjet ink according to any one of 1 to 5, wherein the active energy ray-curable inkjet ink contains a pigment and a pigment dispersant.

7. The inkjet recording method using an active energy ray-curable inkjet ink according to 6, wherein the pigment is pigment particles having an average particle size of 10 to 150 nm.

8. The active energy ray-curable ink according to any one of 1 to 7, wherein the active energy ray-curable inkjet ink has a viscosity of 5 to 5 OmPa · s at 25 ° C. Inkjet recording method using chemical ink jet ink.

9. The ink-jet recording method using the active energy ray-curable ink-jet ink according to any one of 1 to 8, wherein the water content of the pretreatment layer is 0.01 to 5 mass%. .

10. The recording force of the active energy ray-curable ink-jet ink according to item 1, wherein the pretreatment layer has a thickness of 0.001 111 to 2111.

11. A pretreatment is performed using the pretreatment agent, and a step of forming a pretreatment layer and a step of performing recording by discharging an activated energy one-line curable inkjet ink onto the pretreatment layer are continuously performed. 11. The inkjet recording method using the active energy single-line curable inkjet ink according to any one of 1 to 10, wherein the inkjet recording method is performed as described above.

12. The method according to claim 1, wherein the substrate has a step of heating the substrate after the step of forming a pretreatment layer by performing a pretreatment using the pretreatment agent. An inkjet recording method using an active energy single-line inkjet ink.

13. An active energy ray curable ink jet recording apparatus, which is used in an ink jet recording method using the active energy ray curable ink jet ink according to item 1 above.

The invention's effect

[0012] According to the present invention, the active energy line curable type ink jet ink that has high productivity, low cost, no bleeding, high image quality, and excellent substrate adhesion can be printed. An ink jet ink recording method and an active energy one-line curable ink jet ink recording apparatus used therefor can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The recording method of the active energy ray-curable ink jet ink (hereinafter also simply referred to as ink jet ink or ink) of the present invention performs pretreatment using a pretreatment agent on the surface of a base material to form a pretreatment layer. An inkjet recording method comprising a step of forming and a step of recording by discharging an active energy ray-curable inkjet ink onto the pretreatment layer, wherein the pretreatment agent is a polymer latex. It has been found that, by adopting the above-described configuration, a recording method of an active energy ray-curable inkjet ink capable of performing printing with high image quality and excellent substrate adhesion without bleeding can be realized.

[0014] The following is a detailed description of the best mode for carrying out the present invention. The present invention is not limited to these.

[0015] In the recording method of the active energy ray-curable inkjet ink of the present invention, as described above, the polymer latex is used as a pretreatment agent on the surface of the substrate (recording medium). Process.

[0016] The method used for this pretreatment is, for example, a method using a coating process such as spray coating, roll coating, gravure coating, air knife coating, extrusion coating, curtain coating, wire bar coating, or felt coating, or the like. Power to use inkjet method In the present invention, an inkjet method is preferred.

[0017] In the ink jet method, the pretreatment layer can be applied only to the portion where the active energy ray curable ink jet ink is discharged.

[0018] The polymer latex is a dispersion in which a polymer compound (polymer) is dispersed in a solvent.

, Styrene 'butadiene copolymer, acrylonitrile' butadiene copolymer, polyisoprene, polybutadiene, polyurethane, polyacrylic acid, polysalt-vinyl, and other high molecular compounds (polymers) dispersed in water with activator, protective colloid, etc. The known polymer latex is preferably used.

In the present invention, it is preferable that the polymer latex contains a high molecular compound (polymer) having a cationic polymerization reactive group.

The cationic polymerization reactive group is a group capable of reacting with a cationic polymerizable active species, and examples thereof include groups having an ether bond such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group, and these are preferably used.

Specifically, JP-A-5-39324, JP-A-5-93071, JP-A-5-148796, JP-A-5-247381, JP-A-6-92047, JP-A-6-179707, JP-A-6-258771, JP-A-7-26170, JP-A-7-28181, JP-A-7-138304, JP-A-8-106142, column 2000-63406, column 2002-144707, column 20 Those described in each publication of No. 03-246821 can be used.

[0021] Further, commercially available polymer latexes described below are also used. SB (styrene 'butadiene) latex 0561, 0589, 0602, 2108, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, AE (acrylic emulsion) AE116, AE119, AE120, AE121, AE125, AE134, AE137, AE140, AE173, AE200, AE311, AE318, AE3 37, AE343, AE362, AE373, AE379, AE315, AE517, AE604, AE610, AE815, AE866, AE945, AE950, AE986A (manufactured by _hJSR), Polyzole (EV A, SUM, PSA, ROY) (made by Showa Polymer Co., Ltd.), styrene-butadiene latex (Nipol LX407AS series, Nipol LX407F series, Nipol LX407G series, Nipol LX407H series, Nipol LX407K series, Nipol LX407S series, Nipol 2518FS series, SB LATEX, Nipol

2518GL, Nipol LX603, Nipol LX110, Nipol LX112), Polybutadiene and Low Styrene 'Butadiene (Nipol LX112A2, Nipol LX111H, Nipol LX11 INF, Nipol LX111K, Nipol C4850A), Acrylonitrile' Butadiene Latex (Nipol 1561, Nipol 1562) , Nipol 1571H, Nipol 1571C, Nipol 1571C L, Nipol LX517A, Nipol 1577, Nipol LX511A, Nipol LX513), akulate latex (Nipol LX811H, Nipol LX814, Nipol LX851C, Nipol LX 85 IE, Nipol LX851F, Nipol LX852 Nipol LX854E, Nipol LX855EX1, Nipol LX857X2, Nipol LX874), soap-free latex (Nipol SX1105, Nipol SX1503, Nipol SX1706) (manufactured by Enomoto ZEON Co., Ltd.) Nylon resin emulsion, Epoxy Nylon emulsion (above made by Nippon Sci Co., Ltd.), KATHONRLX, KATHON RLXE, KORDEKRMLX (above Over-time & Haas Co., Ltd.).

[0022] When an inkjet method is used as a pretreatment method for the substrate surface, the viscosity of the polymer latex is preferably 1 OmPa · s or less at 55 ° C.

[0023] Furthermore, in order to improve the drying property of the polymer latex, an extremely small amount of an organic solvent may be added. In this case, it is effective to add the cured film in such a range that the solvent resistance and VOC problem do not occur, and the amount thereof is 0.1 to 5% by mass, preferably 0.1 to 3% by mass. [0024] The pretreatment film is formed on the base material by the pretreatment using the polymer latex. From the viewpoint of preventing image quality deterioration due to bleeding of the active energy ray curable inkjet ink, the active energy ray curable inkjet is used. It is preferable that the water content becomes 0.01 to 5% by mass before ink is ejected! /.

[0025] Therefore, in the present invention, for example, a heat drying step is preferably provided between the step of forming the pretreatment layer with the polymer latex and the step of discharging the activated energy one-line curable inkjet ink.

[0026] The film thickness of the pretreatment layer formed of the polymer latex is a force depending on the type of substrate.

It is preferably larger than 1 μm and not larger than 2 μm, more preferably from 0.01 to 1 μm.

Next, the power described above in the form of the inkjet recording method (image forming method) in the present invention is not limited to this.

[0028] << Inkjet Image Forming Method No. 1 >>

• Polymer latex coating process 1: Roll coating

• Polymer latex drying process 1: Roll heating

• Inkjet ink ejection process: common

• Polymer latex coating process 2: Inkjet method

• Polymer latex drying process 2: Infrared heating

• Inkjet ink ejection process: common

• Polymer latex coating process 3: Immersion coating

• Polymer latex drying process 3: microwave heating

• Inkjet ink ejection process: common

Next, details of the active energy ray-curable inkjet ink according to the present invention will be described.

[0029] The ink according to the present invention is preferably an ink containing a force that is an active energy ray-curable ink, in particular, a cationic polymerization compound, and as the cationic polymerization compound, It is preferably at least one selected from an oxetane ring-containing compound, an oxsilane group-containing compound, and a vinyl ether compound.

[0030] The oxysilane group-containing compound according to the present invention is a compound having one or more oxysilane rings represented by the following formula in a molecule, and is usually used as an epoxy resin. Any monomer, oligomer or polymer can be used.

[0031] [Chemical 1]

Specific examples include conventionally known aromatic epoxides, alicyclic epoxides, and aliphatic epoxides. Hereinafter, the epoxide means a monomer or an oligomer thereof. These compounds may be used alone or in combination of two or more as required.

[0033] A preferable aromatic epoxide is a di- or polyglycidyl produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin. Ethers such as di- or polyglycidyl ethers of bisphenol A or its alkylene oxide adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak type Examples include epoxy resin. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0034] As the alicyclic epoxide, a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring can be obtained by epoxy polymerization with an appropriate oxidizing agent such as hydrogen peroxide or peracid. Specific examples of preferred cyclohexene oxide or cyclopentene oxide-containing compounds are, for example, manufactured by Daicel Chemical Industries, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2080, Sepoxide , 3000, Sepide 2000, Evry GT301, Evry GT302, Jeho. Lead GT401, Epolide GT403, EHPE-3150, EHPEL3150CE, union force manufactured by BYBIDE, UVR-6105, UVR-6110, UVR-6128, UVR-6100, UVR-6216, UVR-6000, etc. [0035] Preferable aliphatic epoxides include aliphatic polyhydric alcohols or di- or polyglycidyl ethers of their alkylene oxide adducts, and typical examples thereof include diglycidyl ethers of ethylene glycol. Polyglycerides such as diglycidyl ethers of propylene glycol or diglycidyl ethers of alkylene glycols such as diglycidyl ether of 1,6-hexanediol, di- or triglycidyl ethers of diglycidyl ether of glycerin or its alkylene oxide Polyalkylene group such as diglycidyl ether of glycidyl ether, polyethylene glycol or alkylene oxide-encased diglycidyl ether, polypropylene glycol or diglycidyl ether of alkylene-oxide encased oxide Examples include recalled diglycidyl ether. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

In addition to these compounds, monoglycidyl ethers of higher aliphatic alcohols and phenols, monoglycidyl ethers of talesol, and the like can also be used. Of these epoxides, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in view of fast curing.

[0037] The oxysilane group-containing compound is blended in the ink in an amount of 10 to 50% by mass, preferably 30 to 50% by mass, from the standpoint of durability as a printed matter and ejection properties.

[0038] Examples of the oxetane ring-containing compound according to the present invention include compounds having one or more oxetane rings in the molecule.

[0039] Examples of the compound having one oxetane ring in the molecule include compounds represented by the following general formula (1).

[0040] [Chemical 2] General formula (1>

In the above general formula (1), Z is an oxygen atom or a sulfur atom, R ¹ is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, or a butyl group. Group, fluoroalkyl group having 1 to 6 carbon atoms, allyl group, aryl group, furyl group or chenyl group, R ² is alkyl having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group or butyl group Group, 1-propyl group, 2-prop group, 2-methyl-1-probe group, 2-methyl-2-probe group, 1-buture group, 2-buture group, 3-buture group, etc. Alkyl group having 1 to 6 carbon atoms, phenyl group, benzyl group, fluorinated benzyl group, methoxybenzyl group or phenoxychetyl group, propyl group carbonyl group, butyl carbonyl group or pentyl carbo group 1-6 carbon atoms such as alkyl group, ethoxy carbo yl group, propoxy carbonyl group or butoxy carbo ol group, etc. Moyl group It represents a propyl force Rubamoiru or butyl pentylcarbamoyl alkoxy force Rubamoiru group having 1 to 6 carbon atoms such as a group.

As the oxetane ring-containing compound according to the present invention, in the above general formula (1), R ¹ is a lower alkyl group, particularly an ethyl group, R ² is a butyl group, a phenyl group or a benzyl group, Z is preferably an oxygen atom.

[0043] Examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following general formulas (2) to (8).

[0044] [Chemical 3] General formula (2)

[0045] In the general formula (2), m represents 2, 3 or 4, Z represents an oxygen atom or a sulfur atom, represents a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl group having 1 to 6 carbon atoms, the phenyl group, the fluoroalkyl group having 1 to 6 carbon atoms, the aryl group, the aryl group or the furyl group, R ⁴ is, for example, a carbon represented by the general formula (3). A linear or branched alkylene group of the number 1 to 12, a linear or branched poly (alkyleneoxy) group,

[0046] [Chemical 4] —General formula (3>

[Wherein, R ⁵ represents a lower alkyl group such as a methyl group, an ethyl group, or a propyl group. Or a multivalent group in which a group force consisting of the following general formulas (4), (5) and (6) is also selected.

[0048] [Chemical formula 5] General formula (4)

— (CH ₂ ) ₃ -Si-0-(Si-0) _n -Si— (CH ₂ ) ₃ —

l Re

[0049] In the general formula (4), n is 0 or an integer of 1 to 2000, R ⁶ is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, and the following general formula (7) represents a group selected from the group consisting of:

[0050] [Chemical 6] General formula (5)

[Wherein j is 0 or an integer of 1 to 100, R ⁸ is alkyl having 1 to 10 carbon atoms, is a carbon number of 1 to 10 such as a methyl group, an ethyl group, a propyl group or a butyl group. Represents an alkyl group. ]

[0052] [Chem. 7] General formula (6)

In the general formula (5), R ⁹ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group. It represents an alkyl group having 1 to 10 carbon atoms such as a til group, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxylate group or a strong carboxyl group.

[0054] [Chemical Formula 8] General formula (7)

I I

— 0- (Si-0) j-Si— (CH ₂ ) ₃ —

F¾ Ra

[0055] In the general formula (6), R ^1G represents an oxygen atom, a sulfur atom, NH, SO, SO, CH, C (CH)

Represents 2 2 3 2 or C (CF).

3 2

[0056] As the oxetane ring-containing compound according to the present invention, in the above general formula (2), R ³ is a lower alkyl group, particularly an ethyl group, and R ⁴ is a general formula (5). R ⁹ is a hydrogen atom group, hexamethylene group, in general formula (3), R ⁵ is an ethyl group, R ⁷ and R ⁸ are each a methyl group, and Z is preferably an oxygen atom.

[0057] [Chemical 9] General formula (8)

[0058] In the above general formula (8), r is an integer of 25 to 200, and R is an alkyl group having 1 to 4 carbon atoms or a trialkylsilyl group.

[0059] In the present invention, the cationically polymerizable ink may be a combination of two or more compounds having one or more oxetane rings in the molecule.

[0060] The oxetane ring-containing compound is 50 to 50% from the viewpoint of resistance to printing as a printed matter and ejection properties. 90 mass%, preferably 50-70 mass% is blended.

[0061] The butyl ether compound contained in the ink according to the present invention includes, for example, ethylene glycol monoresinino enoate, ethylene glycol mono vinyl enoate, diethylene glycol divinino ether, triethylene glycol oleore. Monovininole ether, Triethylene glycol divinyl ether, Propylene glycol divinyl ether, Dipropylene glycol dibule ether, Butanediol dibule ether, Hexanediol divinylenothere, Cyclohexanedimethanol divinyl ether, Hydroxyethyl mono bi vinyl ether, hydroxyethyl monovinyl ether, di- or tri Bulle ether compounds such as trimethylolpropane trivinyl ether, Echirubi - ether, _n - butyl Rubi - Rue , Isobutyl vinyl ether, octadecyl vinyl ether, cyclohexenolevinoleateol, hydroxybutinorevininoreetherenore, 2-ethinorexenolevinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples include isopropenyl ether, propylene strength, monobutyl ether compounds such as carbonate, dodecyl vinyl ether, diethylene glycol monobutyl ether, and octadecyl vinyl ether.

[0062] Among these vinyl ether compounds, in consideration of curability, adhesion, and surface hardness, dibyl ether compounds or tribule ether compounds are preferred, particularly divinyl ether compounds. I like it.

[0063] In the present invention, one of the above vinyl ether compounds may be used alone, or two or more may be used in appropriate combination.

[0064] The bull etheric compound is an optional blending component, and by blending it, it is possible to realize a low viscosity required for the ink jet ink. Also, the curing rate can be improved. The beer ether compound is preferably blended in an amount of 0 to 40% by mass, preferably 0 to 20% by mass, in a liquid component comprising an oxysilane group-containing compound and an oxetane ring-containing compound. That's right.

[0065] The ink according to the present invention preferably contains an optical power thione polymerization initiator together with the cationically polymerizable compound.

[0066] Examples of the photopower thione polymerization initiator that can be used in the present invention include arylsulfurium. Salt derivatives (eg, Union Carbide Cyracure UVI-6990, Cyracure UVI-6974, Asahi Denka Kogyo Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adeka Optomer SP—172, etc.), allylo-um salt derivatives (eg, RP-2074 from Rhodia), allene-ion complex derivatives (eg, Irgacure 261, etc. from Ciba Geigy), diazo-um And acid generators such as salt derivatives, triazine initiators and other halogenated compounds.

[0067] The photothion polymerization initiator is preferably contained in a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass of the compound having an alicyclic epoxy group in the ink. If the content of the light power thione polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, no further effect of improving curability can be expected. These light thione polymerization initiators can be used alone or in combination of two or more.

[0068] In the ink according to the present invention, a photopolymerization accelerator can be used, and examples thereof include anthracene and anthracene derivatives (for example, Adekaobomer SP-100 manufactured by Asahi Denki Kogyo Co., Ltd.). These photopolymerization accelerators can be used alone or in combination.

[0069] The ink according to the present invention preferably contains a pigment and a pigment dispersant as a coloring material.

[0070] Examples of the pigment that can be used in the ink according to the present invention include achromatic inorganic pigments such as carbon black, titanium oxide, and calcium carbonate, or chromatic organic pigments.

[0071] Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow, and pyrazolone red, and soluble pigments such as ritole red, heliobolde I, pigment scarlet, and permanent red 2B. Derivatives from vat dyes such as zopigments, alizarin, indanthrone, thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene red and perylene Perylene-based organic pigments such as a single let, isoindolinone-based organic pigments such as isoindolinone yellow and isoindolinone orange, and pyranthrones such as pyranthrone red and pyranthrone orange Organic pigments, thioindigo organic pigments, condensed azo organic pigments, benzimi Dazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments include Flavanthrone yellow, asylamide yellow, nickel azo yellow, copper azomethine yellow, Examples include perinone orange, anthrone orange, dianthraquinol red, and dioxazine violet.

[0072] Further, when organic pigments are exemplified by color index (C.I.) numbers,

C. I. Big Men 卜 Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 109, 110,

117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155

, 166, 168, 180, 185

C. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61

CI pigment red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240

C. I. Pigment Noorette 19, 23, 29, 30, 37, 40, 50

C. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64

C. I. Pigment Green 7, 36

C. I. Pigment Brown 23, 25, 26, etc.

[0073] Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments Pigments and the like are preferable because of their excellent light resistance. The organic pigment is preferably a pigment having an average particle diameter of 10 to 150 nm as measured by laser scattering.

[0074] When the average particle size of the pigment is less than 10 nm, the light resistance is lowered due to the small particle size, and when it exceeds 150 nm, it is difficult to maintain stable dispersion, and the pigment is likely to precipitate. Become.

[0075] The so-called dispersion treatment of the organic pigment can be performed by the following method. That is, a mixture having at least three component powers of an organic pigment, a water-soluble inorganic salt of 3 mass times or more of the organic pigment, and a water-soluble solvent is made into a clay-like mixture and kneaded strongly with a kneader or the like. Then, it is refined and poured into water, and stirred with a high speed mixer to make a slurry. Next, the slurry-like mixture is repeatedly filtered and washed with water to remove the water-soluble inorganic salt and the water-soluble solvent. In the miniaturization step, rosin, pigment dispersant and the like may be added. Examples of water-soluble inorganic salts include sodium chloride sodium and potassium salt potassium. These inorganic salts are preferably used in the range of 3 to 20 times the organic pigment. When the amount of the inorganic salt is less than 3 times by mass, pigment particles having a desired size cannot be obtained. On the other hand, when the amount is more than 20 times by mass, the cleaning process in the subsequent process is great, and the substantial amount of the organic pigment is reduced.

[0076] The water-soluble solvent is used to form an appropriate clay state between the organic pigment and the water-soluble inorganic salt used as a crushing aid, and to perform sufficient crushing efficiently, and is a solvent that dissolves in water. Although it will not specifically limit if it is a chemical | medical agent, Since the temperature rises at the time of kneading | mixing and it will be in the state which a solvent evaporates easily, a high boiling point solvent with a boiling point of 120-250 degreeC is preferable from a safety point. Examples of water-soluble solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isobenzyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycolenomonomethylenoateolene, and diethyleneglycolanol. Monoethylenoatenole, diethyleneglycololebutanolate ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy 2-propanol, 1 ethoxy 2-propanol, dipropylene glycol, dipropylene Examples include glycol monomethyl ether, dipropylene glycol monoethyl ether, and low molecular weight polypropylene alcohol.

In the present invention, the pigment is preferably contained in the ink jet ink in an amount of 3 to 15% by mass in order to obtain a sufficient concentration and sufficient light resistance.

[0078] The pigment dispersant preferably used in the present invention includes a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high-molecular weight acid ester, a salt of a high-molecular-weight polycarboxylic acid, a long-chain polyaminoamide and a polar acid ester. Salt, high molecular weight unsaturated acid ester, high molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester-type cation activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt , Polyoxyethylene alkyl phosphate ester, polyoxyethylene norf Examples include ether, stearylamine acetate, and pigment derivatives.

[0079] Specific examples of the pigment dispersant include “Anti Terra-U (polyaminoamide phosphate)”, “Anti Terra-203Z204 (high molecular weight polycarboxylate)” manufactured by BYK Chemie, “Di sperbyk- 101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 1 64, 165, 166, 170 (Polymer copolymer) ”,“ 400 ”,“: Bykumen ”(high molecular weight unsaturated acid ester),“ BYK— P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104 S, 240S ( High molecular weight unsaturated acid polycarboxylic acid and silicon) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid and silicon) ”and the like.

[0080] In addition, "F force 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766" manufactured by Efka CHEMICALS, "F force polymer 100 (modified polyacrylate) ), 150 (Aliphatic modification '14 positive mer), 400, 401, 402, 403, 450, 451, 452, 453 (Modification '14 positive rate), 745 (Copper phthalocyanine) ", manufactured by Kyoeisha “Floren Ding 0—710 (uretan oligomer)”, “Flonon SH—290, SP—1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS by Enomoto Kasei Co., Ltd.” — 860, 873SN, 87 4 (polymer dispersant), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester type) ”.

[0081] Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN—B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol: L-18 (polycarboxylic acid type polymer) "," Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nouryl ether) "," Acetamine 24 (coconut tamine amine acetate), 86 (Stearylamine amine) ", Zeneca's" Solspers 5000 (phthalocyanine ammonium salt), 13240, 13940 (polyesteramine amine), 17000 (fatty acid amine), 24000, 32000 ", Fluorescent Chemical “-KKol T106 (polyoxyethylene sorbitan monooleate), MYS—IEX (polyoxyethylene monostearate), Hexagline 4—0 (hexaglyceryl tetra) Oleate) "and the like.

[0082] In the ink according to the present invention, the pigment dispersant is preferably contained in the ink in the range of 0.1 to L0 mass%. [0083] The ink-jet ink according to the present invention is produced by well dispersing the pigment together with an active energy ray-curable compound and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with an active energy ray-curable compound. Sufficient dispersion is possible even with dispersion using a normal disperser, so excessive dispersion energy is not used and a great amount of dispersion time is not required. Therefore, an ink having excellent stability that hardly deteriorates when the ink component is dispersed is prepared. The ink is preferably filtered through a filter having a pore size of 3 μm or less, more preferably 1 μm or less.

[0084] In the ink-jet ink according to the present invention, it is preferable to adjust the viscosity at 25 ° C to be as high as 5 to 50 mPa · s from the viewpoint of ejection stability. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C exhibits stable ejection characteristics even from a head having a normal frequency of 4 to 10 kHz to a head having a high frequency of 10 to 50 kHz.

[0085] In addition, the ink-jet ink according to the present invention is preferably used for a piezo head with an electric conductivity of 10 μS / cm or less and without electrical corrosion inside the head. ,.

[0086] Further, in the continuous type, it is necessary to adjust the electric conductivity with an electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mSZcm or more.

[0087] As the base material (recording medium) used in the present invention, all of a wide range of synthetic resins conventionally used in various applications are targeted. Specifically, for example, polyester, polysalt vinyl Nyl, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, etc. The thickness and shape of these synthetic resin substrates Is not limited at all.

In the present invention, ink is first supplied to the printer head of an ink jet recording system printer, discharged from the printer head onto a substrate, and then irradiated with active energy rays such as ultraviolet rays or electron beams. As a result, the ink on the recording medium is quickly cured.

[0089] As the light source of the active energy ray, when irradiating ultraviolet rays, for example, mercury arc lamp, xenon arc lamp, fluorescent lamp, carbon arc lamp, tungsten Halogen copying lamps and sunlight can be used. When cured with an electron beam, it is usually cured with an electron beam with an energy of 300 eV or less, but it can also be cured instantaneously with an irradiation dose of 1 to 5 Mrad.

Example

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Moreover, the part and% in an Example show a mass part and mass%, respectively.

[0091] << Preparation of ink >>

The pigment (P1) and dispersant (S32000) listed in Table 1 were combined with the oxetane ring-containing compound (OX211), the oxsilane group-containing compound (CEL2021P), and the bull etheric compound (DVE-3). After putting in a sand mill and dispersing for 4 hours, each active energy ray-curable ink stock solution was obtained. Next, light power thione polymerization initiator (SP-152) is added to each ink stock solution, gently mixed until the light power thione polymerization initiator is dissolved, and then this is pressure filtered through a membrane filter. An active energy ray-curable inkjet ink was obtained. In addition, the numerical value of the bottom line of Table 1 represents a mass part.

[0092] [Table 1]

[0093] The details of each additive described in Table 1 are as follows.

• Pigment (P1):

Crude copper phthalocyanine (Toyo Ink Mfg. Co. copper phthalocyanine) 250 parts Sodium chloride 2500 parts

160 parts of polyethylene glycol (polyethylene glycol 300, manufactured by Tokyo Chemical Industry Co., Ltd.) The above materials were placed in 5.51 L (1 gallon) of styrene (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture is poured into 2.5 liters of warm water, heated to about 80 ° C and stirred for about 1 hour with a high speed mixer to form a slurry, followed by filtration, Washing with water was repeated 5 times to remove sodium chloride and solvent, followed by spray drying to obtain Pigment P1.

• Oxetane ring-containing compound (OXT-221): Di [1 ethyl (3oxetal)] methyl ether, manufactured by Toagosei Co., Ltd.

• Oxylan group-containing compound (CEL2021P): Alicyclic epoxy compound manufactured by Daicel. 'Bulur ether compound (DVE-3): Triethylene glycol dibul ether manufactured by ISP.

• Pigment dispersant (S32000): Aliphatic modified dispersant Solspurs 32000

'Light power thione polymerization initiator (SP-152): Triphenylsulfurium salt Adekaoptomer SP-152 manufactured by Asahi Denka Co., Ltd.

[0094] << Evaluation Method >>

[Preparation of printed matter]

The ink is printed on polyethylene terephthalate and pre-treated polyethylene terephthalate (base material) using an inkjet printer with a piezo head, and then the substrate is printed on a UV irradiation device (8 cold-cathode tubes: 20 W output). Curing was carried out at a conveying speed of 500 mmZ seconds to produce a printed matter.

[0095] [Curing property]

After UV irradiation, the cured surface was touched with a finger to evaluate whether the tack remained or not.

○: Ink cannot be removed.

X: Ink can be removed.

[0096] [Membrane strength]

The strength of the cured film was determined by a nail pull test.

○: The printed image cannot be taken even if it is pulled.

Δ: Print image is slightly removed when pulled strongly.

X: The printed image can be easily removed by pulling.

[0097] [Adhesion] For the printed image produced above, a sample that does not scratch the printed surface at all, and in accordance with JIS K 540 0, 11 cuts are made on the printed surface vertically and horizontally at lmm intervals, and a 1 mm square board. Samples with 100 eyes were prepared, cellotape (registered trademark) was pasted on each printed surface, quickly peeled off at an angle of 90 degrees, and the remaining print image or grid pattern remaining as shown below. Evaluation was performed according to Use a sample cured at 25 ° C 45% RH. ○: No peeling of the printed image was observed even in the cross-cut test.

Δ: A force that allows slight ink peeling in the cross-cut test. If the ink surface is not scratched, almost no peeling is observed! /.

X: In both conditions, peeling with cello tape (registered trademark) is easily recognized.

[0098] [Image bleeding]

(Double-circle): There is no bleeding and printability is also favorable.

◯: Slight bleeding and printing disturbance occur.

Δ: Although there is bleeding, the characters can be identified.

X: Characters cannot be identified due to bleeding.

[0099] The results are shown in Table 2.

[0100] [Table 2]

[0101] Nos. 1 to 3 of the ink jet recording method (image forming method) in Table 2 represent the forms of the ink jet recording method.

[0102] 《Comparative example》

[Corona treatment]

Using a 6KVA model of a solid state corona treatment machine manufactured by Villa Company, both sides of the support were treated at room temperature for 20mZ. This was designated as Comparative Example 1. [0103] current at this time from the reading value of the voltage, the support processing 0. 375Κν · Α · min Zm ² have been made Kotogawakaka ivy. At this time, the treatment and frequency were 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[0104] [UV curable undercoat]

Ink composition power of the example of the present invention The pigment was removed and the composition was adjusted in the same manner as the ink of the example, and this was designated as Comparative Example 2. In addition, Comparative Example 3 was used without any pretreatment.

[0105] From the results shown in Table 2, it can be seen that the recording method of the present invention enables printing with high productivity, low cost, no bleeding, and high image quality and excellent substrate adhesion.

Claims

The scope of the claims

[1] A step of forming a pretreatment layer on the surface of the base material by using a pretreatment agent and a step of performing recording by discharging an active energy ray-curable inkjet ink onto the pretreatment layer. An inkjet recording method using an active energy ray-curable inkjet ink, characterized in that the pretreatment agent is a polymer latex.

[2] The inkjet recording method using an active energy ray-curable inkjet ink according to [1], wherein the polymer latex contains a polymer compound having a cationic polymerization reactive group.

[3] The inkjet recording method using an active energy ray-curable inkjet ink according to claim 1 or 2, wherein the active energy ray-curable inkjet ink contains a cationic polymerizable compound.

[4] Any one of claims 1 to 3, wherein the cationically polymerizable compound is at least one selected from an oxetane ring-containing compound, an oxsilane group-containing compound, and a bull ether compound. An ink jet recording method using the active energy ray-curable ink jet ink according to the item.

[5] The active energy ray-curable inkjet ink according to any one of claims 1 to 4, wherein the active energy ray-curable inkjet ink contains a light-power thione polymerization initiator. Inkjet recording method.

[6] The active energy ray-curable inkjet ink according to any one of claims 1 to 5, wherein the active energy ray-curable inkjet ink contains a pigment and a pigment dispersant. Inkjet recording method.

7. The inkjet recording method using an active energy ray-curable inkjet ink according to claim 6, wherein the pigment is pigment particles having an average particle size of 10 to 150 nm.

[8] The active energy according to any one of claims 1 to 7, wherein the active energy ray-curable inkjet ink has a viscosity of 5 to 50 mPa's at 25 ° C. An inkjet recording method using a one-line curable inkjet ink.

[9] The active energy ray-curable inkjet ink according to any one of claims 1 to 8, wherein the moisture content of the pretreatment layer is 0.01 to 5% by mass. Inkjet recording method.

[10] The active energy ray-curable inkjet according to any one of [1] to [9], wherein the film thickness of the pretreatment layer is 0.001 μm to 2 μm. Inkjet recording method using ink.

[11] A step of performing a pretreatment using the pretreatment agent and a step of forming a pretreatment layer and a step of performing recording by discharging an active energy one-line curable inkjet ink onto the pretreatment layer are continuously performed. The inkjet recording method using the active energy ray-curable inkjet ink according to any one of claims 1 to 10, wherein the inkjet recording method is an inkjet recording method.

[12] The method according to any one of claims 1 to 11, further comprising a step of heating the substrate after a step of forming a pretreatment layer by performing a pretreatment using the pretreatment agent. An inkjet recording method using the active energy ray-curable inkjet ink described in the item.

[13] An active energy one-line curable ink jet recording apparatus, characterized by being used in the ink jet recording method using the active energy ray-curable ink jet ink according to any one of claims 1 to 12.